Curable resin composition for use in water based paint

ABSTRACT

The present invention proposes highly practical curable resin compositions for use in water based paints, which contain no, or much less organic solvent when compared with current organic solvent based paints, and which produce painted surfaces which have excellent curability and weather resistant properties, as well as excellent resistance to solvents, chemicals and water. These curable resin compositions include a compound combining both epoxy and hydrolyzable silyl groups, and a water based product obtained by dispersing or dissolving in water, a tertiary amino vinyl polymer, a vinyl polymer containing both tertiary amino and acidic groups, or an acidic vinyl polymer, which has been either partially or completely neutralized by an acidic or basic compound.

This is a division of application Ser. No. 08/512,706 filed Aug. 8,1995, U.S. Pat. No. 5,985,980.

BACKGROUND OF THE INVENTION

1. Technical Field

The present invention relates to a useful new curable resin compositionfor use in water based paints. In particular, it relates to a curableresin composition, of particular use in paints, which has excellentweather resistant properties, and furthermore provides excellentcurability, and gives excellent resistance against solvents, chemicalsand water. The primary constituents of this curable resin compositioninclude; a water based product obtained by dispersing or dissolving inwater, a tertiary amino vinyl polymer, or vinyl polymer containing bothtertiary amino and acidic functionalities which has been neutralised byan acidic compound, or alternatively, an acidic vinyl polymer, or vinylpolymer containing both tertiary amino and acidic functionalities whichhas been neutralised by a basic compound, and a compound containing bothepoxy and hydrolysable silyl functionalities.

2. Description of the Prior Art

Due to recent worldwide demand for increased environmental conservationmeasures and improvements in workplace conditions, it is becomingnecessary to move away from current organic solvent based paints, topaints which release less organic solvent into the atmosphere. Inaddition, from an energy conservation point of view, paint resins whichwill cross link at room temperature would be most attractive.

In order to fulfill these requirements, aqueous emulsions of a copolymerformed from an unsaturated monomer of the ethylene family and a primaryor secondary amino alkyl (meta) acrylate, with an epoxy silane couplingagent have been proposed (Japanese Patent Application, FirstPublication, No. Sho 61-28543), but the cured coating film from suchcompositions tends to be inferior in terms of its weather resistantproperties.

Furthermore, water based adhesive compositions formed by combining anepoxy silane coupling reagent, with a water based polymer formed byemulsion polymerisation of a vinyl monomer containing either carboxyl ortertiary amino functionalites (U.S. Pat. No. 4,077,932), oralternatively water based coating compositions for use with paper ortextiles (Japanese Patent Application, First Publication, No. Hei1-96270) have also been proposed, but the surface obtained from suchcompositions, in all cases, is inferior, either in terms of water andsolvent resistance, or in terms of surface appearance.

Moreover, alkali soluble adhesive compositions formed by combining asurface active agent and an epoxy silane coupling agent, with an aqueoussolution of a carboxyl vinyl polymer, which is produced either bypolymerisation of a single carboxyl vinyl monomer, or bycopolymerisation of two or more different carboxyl vinyl monomers, havealso been proposed (Japanese Patent Application, Unpublished, No. Hei6-41504), but the surface formed from such compositions is inferior,particularly in terms of its resistance to water and alkalinity.

The limitation then, of the aforementioned water based resins of vinylpolymers containing either emulsifiers or surface active reagents isthat the resultant surfaces inevitably lack resistance to water andother solvents.

SUMMARY OF THE INVENTION

In view of the above problems, it is an object of the present inventionto provide a novel, and highly practical curable resin composition foruse in water based paints, which contains no, or very little, organicsolvent when compared with current organic solvent based paints, andwhich yields a cured film which has excellent weather resistantproperties, as well as resistance to solvents, chemicals and water. Itis a further object of the invention to provide a novel, and highlypractical curable resin composition for use in water based paints whichwill cross link at room temperature.

Accordingly the present invention gives a curable resin composition foruse in water based paints comprising; a water based product (A) obtainedby dispersing or dissolving in water, a tertiary amino vinyl polymer (I)which has been either partially or completely neutralised by an acidiccompound, and a compound (B) containing both epoxy and hydrolysablesilyl groups.

Moreover the present invention gives a curable resin composition for usein water based paints comprising; a water based product (C) obtained bydispersing or dissolving in water, a vinyl polymer (II) containing bothtertiary amino and acidic functionalities to which has been addedsufficient acidic compound so that the molar ratio of acidicfunctionalities in the added acidic compound to the tertiary aminofunctionalities in the vinyl polymer (II) is at least 0.1, and acompound (B) containing both epoxy and hydrolysable silylfunctionalities. Herein the term molar ratio refers to an equivalenceratio, being the ratio of the equivalent numbers of the respectivefunctionalities.a compound (B) containing both epoxy and hydrolysablesilyl groups.

Furthermore the present invention gives a curable resin composition foruse in water based paints comprising; a water based product (D) obtainedby dispersing or dissolving in water, a vinyl polymer (II) containingboth tertiary amino and acidic functionalities to which has been addedsufficient basic compound so that the molar ratio of basicfunctionalities in the added basic compound to acidic functionalities inthe vinyl polymer (II) is at least 0.1, and a compound (B) containingboth epoxy and hydrolysable silyl groups.

In addition the present invention gives a curable resin composition foruse in water based paints comprising; a water based product (E) obtainedby dispersing or dissolving in water, an acidic vinyl polymer (III)which has been partially, or completely, neutralised by a basiccompound, and a compound (B) containing both epoxy and hydrolysablesilyl groups.

Again the present invention gives a curable resin composition for use inwater based paints comprising; a water based product (A) obtained bydispersing or dissolving in water, a tertiary amino vinyl polymer (I)which has been either partially or completely neutralised by an acidiccompound, a compound (B) containing both epoxy and hydrolysable silylfunctionalities, and a compound (F) containing a hydrolysable silylgroup and/or a silanol group, but excluding the compound (B).

Again the present invention gives a curable resin composition for use inwater based paints comprising; a water based product (C) obtained bydispersing or dissolving in water, a vinyl polymer (II) containing bothtertiary amino and acidic groups to which has been added sufficientacidic compound so that the molar ratio of acidic groups in the addedacidic compound to the tertiary amino groups in the vinyl polymer (II)is at least 0.1, a compound (B) containing both epoxy and hydrolysablesilyl groups, and a compound (F) containing a hydrolysable silylfunctionality and/or a silanol functionality, but excluding the compound(B).

Furthermore the present invention gives a curable resin composition foruse in water based paints comprising; a water based product (D) obtainedby dispersing or dissolving in water, a vinyl polymer (II) containingboth tertiary amino and acidic groups to which has been added sufficientbasic compound so that the molar ratio of basic groups in the addedbasic compound to acidic groups in the vinyl polymer (II) is at least0.1, a compound (B) containing both epoxy and hydrolysable silyl groups,and a compound (F) containing a hydrolysable silyl functionality and/ora silanol functionality, but excluding the compound (B).

In addition the present invention gives a curable resin composition foruse in water based paints comprising; a water based product (E) obtainedby dispersing or dissolving in water, an acidic vinyl polymer (III)which has been partially or completely neutralised by a basic compound,a compound (B) containing both epoxy and hydrolysable silyl groups, anda compound (F) containing a hydrolysable silyl functionality and/or asilanol functionality, but excluding the compound (B).

Again the present invention gives a curable resin composition for use inwater based paints comprising; a water based product (A) obtained bydispersing or dissolving in water, a tertiary amino vinyl polymer (I)which has been either partially or completely neutralised by an acidiccompound, a compound (B) containing both epoxy and hydrolysable silylgroups, and a curing catalyst (G).

Moreover the present invention gives a curable resin composition for usein water based paints comprising; a water based product (C) obtained bydispersing or dissolving in water, a vinyl polymer (II) containing bothtertiary amino and acidic groups to which has been added sufficientacidic compound so that the molar ratio of acidic groups in the addedacidic compound to the tertiary amino groups in the vinyl polymer (II)is at least 0.1, a compound (B) containing both epoxy and hydrolysablesilyl groups, and a curing catalyst (G).

Furthermore the present invention gives a curable resin composition foruse in water based paints comprising; a water based product (D) obtainedby dispersing or dissolving in water, a vinyl polymer (II) containingboth tertiary amino and acidic groups to which has been added sufficientbasic compound so that the molar ratio of basic groups in the addedbasic compound to acidic groups in the vinyl polymer (II) is at least0.1, a compound (B) containing both epoxy and hydrolysable silyl groups,and a curing catalyst (G).

In addition the present invention gives a curable resin composition foruse in water based paints comprising; a water based product (E) obtainedby dispersing or dissolving in water, an acidic vinyl polymer (III)which has been partially or completely neutralised by a basic compound,a compound (B) containing both epoxy and hydrolysable silyl groups, anda curing catalyst (G).

Again the present invention gives a curable resin composition for use inwater based paints comprising; a water based product (A) obtained bydispersing or dissolving in water, a tertiary amino vinyl polymer (I)which has been either partially or completely neutralised by an acidiccompound, a compound (B) containing both epoxy and hydrolysable silylgroups, a compound (F) containing a hydrolysable silyl functionalityand/or a silanol functionality, but excluding the compound (B), and acuring catalyst (G).

Again the present invention gives a curable resin composition for use inwater based paints comprising; a water based product (C) obtained bydispersing or dissolving in water, a vinyl polymer (II) containing bothtertiary amino and acidic groups to which has been added sufficientacidic compound so that the molar ratio of acidic groups in the addedacidic compound to the tertiary amino groups in the vinyl polymer (II)is at least 0.1, a compound (B) containing both epoxy and hydrolysablesilyl functionalities, a compound (F) containing a hydrolysable silylfunctionality and/or a silanol functionality, but excluding the compound(B), and a curing catalyst (G).

Furthermore the present invention gives a curable resin composition foruse in water based paints comprising; a water based product (D) obtainedby dispersing or dissolving in water, a vinyl polymer (II) containingboth tertiary amino and acidic groups to which has been added sufficientbasic compound so that the molar ratio of basic groups in the addedbasic compound to acidic groups in the vinyl polymer (II) is at least0.1, a compound (B) containing both epoxy and hydrolysable silyl groups,a compound (F) containing a hydrolysable silyl functionality and/or asilanol functionality, but excluding the compound (B), and a curingcatalyst (G).

In addition the present invention gives a curable resin composition foruse in water based paints comprising; a water based product (E) obtainedby dispersing or dissolving in water, an acidic vinyl polymer (III)which has been partially or completely neutralised by a basic compound,a compound (B) containing both epoxy and hydrolysable silyl groups, acompound (F) containing a hydrolysable silyl functionality and/or asilanol functionality, but excluding the compound (B), and a curingcatalyst (G).

DETAILED DESCRIPTION OF THE INVENTION

The composition formed by combining compounds which contain both epoxyand hydrolysable silyl groups, with specific aqueous solutions ordispersions of either a tertiary amino vinyl polymer, or a vinyl polymercontaining both tertiary amino and acidic groups which has beenneutralised by an acidic compound, or alternatively, an acidic vinylpolymer, or a vinyl polymer containing both tertiary amino and acidicgroups which has been neutralised by a basic compound, contains littleorganic solvent, displays excellent curability, and also produces acoating film which is highly weather resistant and displays excellentresistance to solvents, chemicals, water and `yellowing` due to heat.

It was predicted that water based products of acid or base neutralisedresins, like those described in this invention, would, upon mixing withcompounds containing epoxy and hydrolysable silyl groups react quickly,either by hydrolysis of the hydrolysable silyl functionality followed bya condensation reaction, resulting in consumption of the hydrolysablesilyl functionality, or alternatively, by a ring opening reaction of theepoxy functionality, and that as a result, the curability of suchmixtures would be inferior, and many of the properties of the resultingcoating film would be affected. In actuality however, as detailed above,both the curability and coating film were of an excellent standard.

That is to say the present invention is a curable resin composition foruse in water based paints made from, a water based product (A) obtainedby dispersing or dissolving in water, a tertiary amino vinyl polymer (I)which has been either partially or completely neutralised by an acidiccompound, and a compound (B) containing both epoxy and hydrolysablesilyl groups.

Moreover the present invention is a curable resin composition for use inwater based paints made from, a water based product (C), obtained bydispersing or dissolving in water, a vinyl polymer (II) containing bothtertiary amino and acidic groups to which has been added sufficientacidic compound so that the molar ratio (also referred to hereunder asthe molar ratio of the acidic groups in the added acidiccompound/tertiary amino groups in the vinyl polymer) of acidic groups inthe added acidic compound to the tertiary amino groups in the vinylpolymer (II) is at least 0.1, and a compound (B), containing both epoxyand hydrolysable silyl groups.

Furthermore the present invention is a curable resin composition for usein water based paints made from; a water based product (D) obtained bydispersing or dissolving in water, a vinyl polymer (II) containing bothtertiary amino and acidic groups to which has been added sufficientbasic compound so that the molar ratio of basic groups in the addedbasic compound to acidic groups in the vinyl polymer (II) is at least0.1, and a compound (B), containing both epoxy and hydrolysable silylgroups.

Additionally the present invention is a curable resin composition foruse in water based paints made from a water based product (E) obtainedby dispersing or dissolving in water, an acidic vinyl polymer (III)which has been partially, or completely, neutralised by a basiccompound, and a compound (B) containing both epoxy and hydrolysablesilyl groups.

Furthermore, this novel and highly practical curable resin compositionfor use in water based paints gives a coating film which has excellentweather resistant, solvent resistant, chemical resistant and waterresistant properties, and compared to current organic solvent basedpaints contains less or no organic solvent.

In the production of the curable resin composition for use in waterbased paints described in this invention, a vinyl polymer is used as therequired base constituent of the resin, that is, the required filmforming constituent. Representative examples of this vinyl polymerinclude acrylic polymers, aromatic vinyl polymers, vinyl ester polymersand fluoro olefin polymers.

Furthermore, of these various vinyl polymers, acrylic polymers andfluoro olefin polymers are particularly suitable.

Of these various vinyl polymers we will firstly explain theaforementioned water based product (A), obtained by dispersing ordissolving in water, a tertiary amino vinyl polymer (I) which has beeneither partially or completely neutralised by an acidic compound.

The aforementioned tertiary amino vinyl polymer (I) can be easilyproduced by standard methods. For example, (1) a method involvingcopolymerising a tertiary amino vinyl monomer with otherco-polymerisable vinyl monomer, or (2) a method as is described inJapanese Patent, First Publication No. Sho 59-56243, involvingdehydrative imidisation processing following the addition reaction of acompound containing both tetiary amino and primary amino groups to avinyl polymer containing an acid anhydride functionality.

There are various suitable production methods, but of these, method (1)above is the most simple and convenient to carry out, and is thus mostsuitable.

Particularly suitable examples of the tertiary amino vinyl monomer{hereafter abbreviated as (a-1)} used to produce the tertiary aminovinyl polymer (I) described in production method (1) above include thevarious (meta) acrylic acid ester monomers such as 2-dimethylamino ethyl(meta) acrylate, 2-diethylamino ethyl (meta) acrylate, 3-dimethylaminopropyl (meta) acrylate, 3-diethylamino propyl (meta) acrylate,N-(2-(meta) acryloyl oxyethyl) piperidine, N-(2-(meta) acryloyloxyethyl) pyrrolidine and N-(2-(meta) acryloyl oxyethyl) morpholine; thevarious aromatic monomers such as 4-(N,N-dimethylamino) styrene,4-(N,N-diethylamino) styrene and 4-vinyl pyridine; the variousacrylamide monomers such as N-(2-dimethylamino ethyl) (meta) acrylamide,and N-(3-dimethylamino propyl) (meta) acrylamide; and the various vinylether monomers such as 2-dimethylamino ethyl vinyl ether, 2-diethylaminoethyl vinyl ether, 3-dimethylamino propyl vinyl ether, 3-diethylaminopropyl vinyl ether, 4-dimethylamino butyl vinyl ether, and6-dimethylamino hexyl vinyl ether.

Particularly representative examples of the other vinyl monomer{hereafter abbreviated as (a-2)} to be copolymerised with the tertiaryamino vinyl monomer (a-1) mentioned above include, the various metaacrylic acid esters such as methyl (meta) acrylate, ethyl (meta)acrylate, n-propyl (meta) acrylate, iso-propyl (meta) acrylate, n-butyl(meta) acrylate, iso-butyl (meta) acrylate, tert-butyl (meta) acrylate,2-ethylhexyl (meta) acrylate, lauryl (meta) acrylate, cyclohexyl (meta)acrylate, benzyl (meta) acrylate, 2-hydroxyethyl (meta) acrylate,2-hydroxypropyl (meta) acrylate, 2-hydroxybutyl (meta) acrylate, and4-hydroxybutyl (meta) acrylate; the various unsaturated di-acidic alkylesters such as dimethyl maleate, dimethyl fumarate, dibutyl fumarate anddimethyl itaconate; the various vinyl monomers containing a carboxylicacid amide functionality such as N,N-dimethyl (meta) acrylamide,N-alkoxymethyl (meta) acrylamides, diacetone (meta) acrylamide, andN-methylol (meta) acrylamide; the various crotonic acid esters such asmethyl crotonate, ethyl crotonate, and n-butyl crotonate; the variousvinyl esters such as vinyl acetate, vinyl benzoate, and Veova (abranched chain mono carboxyl vinyl ester produced by Shell Corporation,Holland); the various vinyl monomers containing nitrile functionalitysuch as acrylonitrile; the various (per)fluoroalkyl vinyl monomers suchas fluoroalkyl (meta) acrylates, perfluoroalkyl (meta) acrylates,perfluoro cyclohexyl (meta) acrylate, di-perfluoro cyclohexyl fumarate,and N-isopropyl perfluorooctane sulfonarnide ethyl (meta) acrylate; thevarious vinyl monomers containing polysiloxane functionality such as CH₂═CHCOO (CH₂)₃ [Si (CH₃)₂ O]_(n) Si (CH₃)₃, CH₂ ═C (CH₃) COOC₆ H₄ [Si(CH₃)₂ ]_(n) Si (CH₃)₃, CH2═C (CH₃) COO (CH₂)₃ [Si (CH₃)₂ O]_(n) Si(CH₃)₃, CH₂ ═C (CH₃) COO (CH₂)₃ [Si (CH₃) (C₆ H₅) O]_(n) Si (CH₃)₃ andCH₂ ═C (CH₃) COO (CH₂)₃ [Si (C₆ H₅)₂ O]_(n) Si (CH₃)₃ (Note that nshould be zero, or any integer between 1 and 130); the varioushalogenised olefins such as vinyl chloride, vinylidine chloride, vinylfluoride, vinylidine fluoride, tetrafluoro ethylene, hexafluoropropylene, and chloro trifluoro ethylene; the various aromatic vinylmonomers such as styrene, α-methyl styrene, p-tert-butyl styrene, andvinyl toluene; and the various vinyl ethers such as ethyl vinyl ether,n-propyl vinyl ether, iso-butyl vinyl ether, 2-ethylhexyl vinyl ether,cyclohexyl vinyl ether, cyclopentyl vinyl ether, 2-hydroxybutyl vinylether, 4-hydroxybutyl vinyl ether, 6-hydroxybutyl vinyl ether,6-hydroxyhexyl vinyl ether.

Furthermore, monomers containing a polyether segment such aspolyethylene glycol mono (meta) acrylate, mono alkoxy polyethyleneglycol (meta) acrylate, polypropylene glycol mono (meta) acrylate,polytetramethylene glycol mono (meta) acrylate, mono alkoxypolypropylene glycol (meta) acrylates, and mono alkoxy polypropyleneglycol (meta) acrylates may also be used with no loss in the weatherresistant or water resistant properties of the final product.

In order to produce the vinyl polymer (I) any of the aforementionedmonomers can be polymerised by any of the standard methods, but radicalpolymerisation in solution is the simplest and most convenient method,and is thus particularly recommended.

Particular suitable solvents to use for this reaction include, thevarious hydrocarbon solvents such as toluene, xylene, cyclohexane,n-hexane, and octane; the various alcohol solvents such as methanol,ethanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, ethyleneglycol monomethyl ether, ethylene glycol mono ethyl ether, ethyleneglycol Imnono iso-propyl ether, and ethylene glycol monobutyl ether; thevarious esters such as methyl acetate, ethyl acetate, n-butyl acetate,and amyl acetate; and the various ketone solvents such as acetone,methyl ethyl ketone, methyl iso-butyl ketone, and cyclohexanone. All ofthese solvents may be used separately or in mixtures of 2 or moresolvents. Water may also be added.

Polymerisation can be carried out by normal methods, using the selectedsolvent and any well known radical polymerisation initiators such as azoor peroxide compounds. Furthermore, if required, chain transfer reagentssuch as lauryl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-mercaptoethanol, thioglycolic acid octyl, 3-mercapto propionic acid, andα-methyl styrene dimer may be used as molecular weight regulatingreagents.

A tertiary amino vinyl polymer (I) produced in this way should containbetween about 0.03 and 2.5 moles of tertiary amino groups per 1000 gramsof solid material, with between 0.05 and 1.5 moles being preferable, andbetween 0.05 and 0.5 moles being most suitable. Furthermore, the averagemolecular weight for the polymer (I) should generally be in the range500-100,000, and preferably in the range 1000-30,000.

Moreover, in cases where hydroxyl functionality is introduced into thetertiary amino vinyl polymer (I), by for example using a monomercontaining a hydroxyl group as a comonomer, then the curability of thisinvention's final composition, which will contain the water basedproduct (A) formed from this polymer (I) as the constituent necessaryfor the formation of the coating film, can be improved one step,producing a coating film which has even better external appearance, evenbetter resistance to solvents, and an even greater level of hardness.

In those instances where hydroxyl functionality is introduced into thetertiary amino vinyl polymer (I), then 1000 grams of solid materialshould contain between 0.04 and 2 moles, and preferably between 0.08 and1.2 moles of hydroxyl groups.

By adding an acidic compound to the tertiary amino vinyl polymer (I)formed by the method mentioned above, the tertiary amino groups in thepolymer are partially, or completely neutralised, and a polymer which issoluble, or dispersible in water is generated.

Particularly representative acidic compounds which can be used in thisinstance include carboxylic acids with between 1 and 10 carbon atomssuch as formic acid, acetic acid, propionic acid, butyric acid, 2-methylbutyric acid, iso-valeric acid, trimethyl acetic acid, glycolic acid andlactic acid; mono- or dialkyl esters of phosphoric acid such asphosphoric acid monomethyl ester, phosphoric acid dimethyl ester,phosphoric acid mono-iso-propyl ester, phosphoric acid di-iso-propylester, phosphoric acid mono2-ethylhexyl ester, and phosphoric aciddi-2-ethylhexyl ester; organic sulfonic acids such as methanesulfonlicacid, propanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid; and various inorganic acids such as hydrochloricacid, sulphuric acid, nitric acid and phosphoric acid. Among the aboveacidic compounds however, the carboxylic acids are the most suitable.

The quantity of acidic compound to be added to the polymer, should be atleast enough to generate dispersibility in the vinyl polymer (I)outlined above, and the molar ratio of the number of acidic groups inthe added acidic compound to the number of amino groups in the polymer,in other words the equivalence ratio: acidic groups in acid I tertiaryamino groups in polymer (I), should be 0.1 or greater, but in order notto lose the properties of the coating film generated, a ratio of between0.1 and 3 is preferred, and a ratio of between 0.1 and 2 is mostsuitable.

The previously mentioned water based product (A), can be generated fromthe thus produced neutralised vinyl polymer (I), using various standardmethods. For example, water can be simply added to the neutralisedmaterial, or alternatively, the material added to water to produce thewater based product.

Furthermore, the water based product (A) can be produced, as required,with either partial, or complete removal of the organic solvent used inthe production of the vinyl polymer (I), by removing the solvent undertemperature, or under reduced pressure.

Next, we will explain the previously mentioned water based product (C),obtained by dispersing or dissolving in water, a vinyl polymer (II)containing both tertiary amino and acidic groups to which has been addedsufficient acidic compound so that the molar ratio of acidic groups inthe added acidic compound to tertiary amino groups in the vinyl polymeris at least 0.1.

This vinyl polymer (II) containing both tertiary amino and acidic groupscan be produced by various standard means. For example, (3) a mixture ofmonomers containing a tertiary amino vinyl monomer and an acidic vinylmonomer can be polymerised, (4) as presented in Japanese Patent, FirstPublication, No. Sho 59-56243, a vinyl polymer containing a carboxylicacid anhydride functionality can be reacted with a compound whichcontains a tertiary amino functionality and a functionality with anactive hydrogen, (5) a vinyl polymer containing hydroxyl and tertiaryamino groups can be reacted with a dicarboxylic acid anhydride, or (6) amixture of monomers containing a tertiary amino vinyl monomer, and avinyl monomer containing a blocked acid functionality such as a trialkylsilyl ester functionality, a hemiacetyl ester functionality, or atert-butyl ester functionality, which can easily be converted to a freeacid functionality by the action of acid, heat or water, can bepolymerised, producing a vinyl polymer with tertiary amino and blockedacid groups, which can then have the blocked acid groups converted tofree acid groups. Among the methods outlined, method (3) is particularlyrecommended, because it is the most simple and convenient. The tetiaryamino vinyl monomer required to produce the vinyl polymer (II)containing both tertiary amino and acidic groups by method (3) above,can be any of the various tertiary amino vinyl monomers (a-1) mentionedpreviously as possible precursors to the tertiary amino vinyl polymer(I).

Furthermore, particularly suitable acidic vinyl monomers {hereafterabbreviated as (a-3)} for the production of this vinyl polymer (II)include (meta) acrylic acid, crotonic acid, maleic acid, itaconic acid,half esters of maleic acid and alkyl alcohols containing between 1 and10 carbon atoms, half esters of itaconic acid and alkyl alcoholscontaining between 1 and 10 carbon atoms, fumaric acid, or half estersof fumaric acid and alkyl alcohols containing between 1 and 10 carbonatoms, citraconic acid, 4-vinyl benzoic acid, cinnamic acid, succinicacid mono 2-(meta) acrylol oxyethyl ester, phthalic acid 2-(meta)acryloyl oxyethyl ester; the various mono vinyl esters of multicarboxylic acids such as malonic acid, adipic acid and sebacic acid; thevarious vinyl monomers containing phosphoric acid functionality such asmono{2-(meta) acryloyl oxyethyl} acid phosphate; and the various vinylmonomers containing sulfonic acid functionality such as p-vinylbenzenesulfonic acid, 2-(meta) acryloyl oxyethanesulfonic acid, 3-(meta)acryloyl oxypropanesulfonic acid, and2-acrylylamido-2-methylpropanesulfonic acid.

Among these, the use of monomers containing carboxylic acidfunctionality is desirable, and (meta) acrylic acid is particularlysuitable.

Furthermore, other copolymerisable vinyl monomers which can be used inthe production of the vinyl polymer (II) include the various vinylmonomers (a-2) previously mentioned in the discussion regardingproduction of vinyl polymer (I).

The use of solvents and initiators in the production of the vinylpolymer (II) from the various aforementioned monomers, follows the samepattern as is described for production of vinyl polymer (I).

A vinyl polymer (II) containing both tertiary amino and acidic groupsproduced in this way should contain between about 0.03 and 2.5 moles oftertiary amino groups per 1000 grams of solid material, with between0.05 and 1.5 moles being preferable, and between 0.05 and 0.5 molesbeing most suitable.

Furthermore, it should contain between about 0.07 and 5.0 moles ofacidic groups, with between 0.07 and 2.0 moles being preferable, andbetween 0.1 and 0.7 moles being most suitable. Moreover, the averagemolecular weight for the polymer (II) should generally be in the range500-100,000, and preferably in the range 1000-30,000.

Furthermore, in cases where hydroxyl functionality is introduced intothe vinyl polymer (II) containing both tertiary amino and acidic groups,by for example using a monomer containing a hydroxyl group as acomonomer, then the curability of this invention's final composition,which will contain the water based product (C) formed from this polymer(II) as the constituent necessary for the formation of the coating film,can be improved one step, producing a coating film which has even betterexternal appearance, even better resistance to solvents, and an evengreater level of hardness.

In those instances where hydroxyl functionality is introduced into thevinyl polymer (II) containing both tertiary amino and acidic groups,then 1000 grams of solid material should contain between 0.04 and 2moles, and preferably between 0.08 and 1.2 moles of hydroxyl groups.

By adding an acidic compound to the vinyl polymer (II) containing bothtertiary amino and acidic groups formed by the method mentioned above,the tertiary amino groups in the polymer are partially, or completelyneutralised, and a polymer which is soluble, or dispersible in water isgenerated.

The acidic compound used in this step can be any of the acidic compoundsmentioned previously as being suitable in the production of the waterbased product (A), but of these, carboxylic acids are the most suitable.

The quantity of acidic compound to be added to the polymer, should besufficient to ensure that the molar ratio of acidic groups in the addedacidic compound to tertiary amino groups in the vinyl polymer (II) is atleast 0.1. A ratio of between 0.1 and 3 is preferred, and a ratio ofbetween 0.1 and 2 is most suitable.

The previously mentioned water based product (C), can be generated fromthe thus produced neutralised vinyl polymer (II) produced by thismethod, by the same methods outlined above for producing the water basedproduct (A) from the neutralised vinyl polymer (I).

Next, we will explain the previously mentioned water based product (D),obtained by dispersing or dissolving in water, a vinyl polymer (II)containing both tertiary amino and acidic functionalities to which hasbeen added sufficient basic compound so that the molar ratio of basicfunctionalities in the added basic compound to acidic functionalities inthe vinyl polymer (II) is at least 0.1.

Firstly, the vinyl polymer (II) containing both tertiary amino andacidic functionalities can be produced by the method already describedin the discussion concerning the production of water based product (C).

Furthermore, in cases where hydroxyl functionality is introduced intothe vinyl polymer (II) containing both tertiary amino and acidic groups,by for example using a monomer containing a hydroxyl group as acomonomer, then the curability of this invention's final composition,which will contain the water based product (D) formed from this polymer(II), can be improved one step, producing a coating film which has evenbetter external appearance, even better resistance to solvents, and aneven greater level of hardness. In those instances where hydroxylfunctionality is introduced into the vinyl polymer (II) containing bothtertiary amino and acidic groups, then 1000 grams of solid materialshould contain between 0.04 and 2 moles, and preferably between 0.08 and1.2 moles of hydroxyl groups.

By adding a basic compound to the vinyl polymer (II) containing bothtertiary amino and acidic groups formed by the method mentioned above,the acidic groups in the polymer are partially, or completelyneutralised, and a polymer which is soluble, or dispersible in water isgenerated.

Particularly representative examples of basic compounds which can beused in this instance include the various organic amines such as methylamine, dimethyl amine, trimethyl amine, ethyl amine, diethyl amine,triethyl amine, n-butyl amine, tri-n-butyl amine, 2-amino-2-methylpropanol, 2-amino ethanol, and 2-dimethylamino ethanol; the variousinorganic basic compounds beginning with ammonia, and including sodiumhydroxide and potassium hydroxide; and quaternary ammonium hydroxidessuch as tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide,trimethyl benzyl ammonium hydroxide.

Among the basic compounds listed, ammonia or the various organic aminesare particularly suitable.

The quantity of basic compound to be added to the polymer, should besufficient to ensure that the molar ratio of basic groups in the addedbasic compound to acidic groups in the vinyl polymer (II) is at least0.1. A ratio of between 0.1 and 3 is preferred, and a ratio of between0.1 and 2 is most suitable.

In order to prepare the water based product (D) from the thus formedmixture of vinyl polymer (II) and basic compound, the same methodsoutlined above for producing the water based product (A) from theneutralised vinyl polymer (I) can be used.

Next, we will explain the previously mentioned water based product (E),obtained by dispersing or dissolving in water, an acidic vinyl polymer(III) which has been partially or completely neutralised by a basiccompound.

This acidic vinyl polymer (III) can be produced by various standardmeans. For example, (7) an acidic vinyl monomer can be copolymerisedwith other co-polymerisable vinyl monomer, (8) a vinyl monomer havinghyroxy group can be reacted with a dicarboxylic acid anhydride, or (9)as was described previously, a vinyl monomer with a blocked acidicfunctionality can be copolymerised with other suitable vinyl polymer,and the blocked acidic functionality then converted to a free acidfunctionality.

Of these methods, method (7) is recommended as it is the simplest andmost convenient.

The acidic vinyl monomer required to produce the acidic vinyl polymer(III) by method (7) above, can of course be any of the various acidicvinyl monomers (a-3) mentioned previously as suitable monomers for theproduction of the vinyl polymer (II) containing both tertiary amino andacidic groups.

Of these, monomers containing carboxylic acid functionality areparticularly suitable.

Furthermore, other copolymerisable vinyl monomers which can be used inthe production of the vinyl polymer (III) include, of course, thevarious vinyl monomers (a-2) previously mentioned in the discussionregarding production of vinyl polymer (I).

Similar solvents, initiators and procedure used in the production of thevinyl polymer (III) are selected, respectively from the representativesmentioned earlier in this invention for production of vinyl polymer (I).

A vinyl polymer (III) produced in this way should contain between about0.07 and 5.0 moles of acidic groups per 1000 grams of solid material,with between 0.3 and 2.0 moles being preferable. Furthermore, theaverage molecular weight for the vinyl polymer (III) should generally bein the range 500-100,000, and preferably in the range 100-30,000.

Moreover, in cases where hydroxyl functionality is introduced into theacidic vinyl polymer (III), by for example using a monomer containing ahydroxyl group as a comonomer, then the curability of this invention'sfinal composition, which will contain the water based product (F) formedfrom this polymer (III) as the constituent necessary for the formationof the coating film, can be improved one step, producing a coating filmwhich has even better external appearance, even better resistance tosolvents, and an even greater level of hardness.

In those instances where hydroxyl functionality is introduced into theacidic vinyl polymer (III), then 1000 grams of solid material shouldcontain between 0.04 and 2 moles, and preferably between 0.08 and 1.2moles of hydroxyl groups.

By adding a basic compound to the acidic vinyl polymer (III) prepared bythe method mentioned above, the acidic groups in the polymer (III) arepartially, or completely neutralised, and then a polymer which issoluble or dispersible in water is generated.

The basic compound used in this step can, of course, be any of thecompounds mentioned previously as being suitable in the production ofthe water based product (D), but among them, ammonia and organic aminesare suitable.

The quantity of basic compound to be added to the polymer, should besufficient to ensure that the molar ratio of basic groups in the addedbasic compound to acidic groups in the vinyl polymer (III) is at least0.1. A ratio of between 0.1 and 3 is preferred, and a ratio of between0.1 and 2 is most suitable.

In order to prepare the water based product (E) from the thus formedmixture of vinyl polymer (III) and basic compound, the similar wayoutlined above for producing the water based product (A) from theneutralised vinyl polymer (I) may be used.

Representative examples of the previously mentioned compound (B), whichcontains both epoxy and hydrolysable silyl groups in the one molecule,include vinyl polymers with both these types of reactive functionality,silane coupling reagent which contains epoxy functionality, and siliconeresins with both types of reactive functionality.

Hydrolysable silyl functionality here, refers to groups of atoms whichcontain a silicon atom which is bonded to, for example, a halogen atom,or an alkoxy, substituted alkoxy, phenoxy, isopropenyloxy, acyloxy oriminooxy functionality, and which are easily hydrolysable to form asilanol functionality. Particularly representative examples include thealkoxy silyl, phenoxy silyl, halo silyl, isopropenyloxy silyl, acyloxysilyl, and iminooxy silyl groups.

Any of the standard methods can be used to produce the vinyl polymerscontaining these two reactive groups, but the recommended methodsinclude; (i) a solution radical copolymerisation of a vinyl monomercontaining a hydrolysable silyl functionality such as γ-(meta) acryloyloxy propyl trimethoxy silane, γ-(meta) acryloyl oxy propyl methyldimethoxy silane, γ-(meta) acryloyl oxy propyl triisopropenyloxy silane,γ-(meta) acryloyl oxy propyl triiminooxy silane, vinyl trimethoxysilane, vinyl triethoxy silane, vinyl (tris-β-methoxy ethoxy) silane,vinyl triacetoxy silane, or vinyl trichloro silane, with a vinyl monomercontaining an epoxy functionality such as glycidyl (meta) acrylate,(β-methyl) glycidyl (meta) acrylate, 3,4-epoxy cyclohexyl (meta)acrylate, aryl glycidyl ether, 3,4-epoxy vinyl cyclohexane, di(β-methyl) glycidyl maleate, or (β-methyl) glycidyl fumarate, where, ifnecessary, solution radical copolymerisation with the variousaforementioned vinyl monomers (a-2) may also be employed, oralternatively, (ii) a solution radical (co)polymerisation of a mixtureof monomers which must include one of the various epoxy vinyl monomersmentioned above, in the presence of one of various chain transfer agentswhich include a hydrolysable silyl functionality, such as γ-mercaptopropyl trimethoxy silane, γ-mercapto propyl triethoxy silane, γ-mercaptopropyl methyldimethoxy silane, γ-mercapto propyl triisopropenyloxysilane, or γ-mercapto propyl triiminooxy silane. Alternatively acombination of the two methods, (i) and (ii) may be used.

Particularly representative examples of the epoxy silane couplingreagent mentioned above include various epoxy silane compounds such asγ-glycidoxy propyl trimethoxy silane, γ-glycidoxy propyl triethoxysilane, γ-glycidoxy propyl methyl dimethoxy silane, γ-glycidoxy propylmethyl diethoxy silane, β-(3,4-epoxy cyclohexyl) ethyl trimethoxysilane, β-(3,4-epoxy cyclohexyl) ethyl methyl diethoxy silane,γ-glycidoxy propyl triisopropenyloxy silane, γ-glycidoxy propyltriiminooxy silane; the addition products of various isocyanato silanecompounds, such as γ-isocyanato propyl triisopropenyloxy silane orγ-isocyanato propyl trimethoxy silane with glycidol; the additionproducts of various amino silane compounds, such as γ-aminopropyltrimethoxy silane with diepoxy compounds; or compounds which contain twoor more hydrolysable silyl groups and two or more epoxy groups in amolecule, formed by a partial hydrolysis condensation of the variousepoxy silane compounds mentioned above.

Particularly representative examples of the aforementioned siliconeresins which contain both epoxy and hydrolysable silyl groups are thecyclic tetra siloxanes, an example of which is shown below. ##STR1##(Note, the Gly in this diagram represents a 3-glycidoxy propylfunctionality)

In the production of the particular curable resin composition for use inwater based paint, detailed in this invention, which contains theaforementioned water based product (A) and compound (B) containing bothepoxy and hydrolysable silyl groups, as the base resin constituents, thetwo constituents (A) and (B) should be mixed together in a proportionthat will yield to typical values for the molar ratio of the number ofmoles of tertiary amino groups in the water based product (A), to thenumber of moles of epoxy groups in compound (B) {hereafter alsodescribed as the molar ratio [tertiary amino groups in water basedproduct (A)/epoxy groups in compound (B)]} of between about 0.1 and 5.0,with a ratio of between 0.3 and 3.0 being preferable, and a ratio ofbetween 0.5 and 2.0 being most suitable.

Furthermore, in the production of the particular curable resincomposition for use in water based paint, detailed in this invention,which contains either of the aforementioned water based products (C) or(D) and compound (B), containing both epoxy and hydrolysable silylgroups as the necessary base resin constituents, the two constituents(C) and (B), or alternatively (D) and (B) should be mixed together in aproportion that will yield typical values for the molar ratio[functionalities (namely, tertiary amino+acidic functionalities) inwater based product (C) or (D)/epoxy functionalities in compound (B)] ofbetween about 0.1 and 5.0, with a ratio of between 0.3 and 3.0 beingpreferable, and a ratio of between 0.5 and 2.0 being most suitable.

In the production of the particular composition, detailed in thisinvention, which contains the water based product (E) and compound (B)containing both epoxy and hydrolysable silyl functionalities as thenecessary base resin constituents, the two constituents (E) and (B)should be mixed together in a proportion that will yield to typicalvalues for the molar ratio [acidic functionalities in water basedproduct (E)/epoxy functionalities in compound (B)] of between about 0.1and 5.0, with a ratio of between 0.3 and 3.0 being preferable, and aratio of between 0.5 and 2.0 being most suitable.

According to another aspect of this invention, addition of a compound(F), which contains a hydrolysable silyl functionality and/or a silanolfunctionality, but excludes the compound (B) which contain both epoxyand silyl functionalities, the weather resistance of the cured coatingfilm obtained is improved, as is the hardness of the surface.

Particularly representative examples of this compound (F), containing ahydrolysable silyl functionality and/or a silanol functionality aresilicate compounds such as methyl silicate, ethyl silicate, isopropylsilicate, and n-butyl silicate; various trifunctional silane compoundssuch as methyl trimethoxy silane, phenyl trimethoxy silane, methyltriethoxy silane, phenyl triethoxy silane, and isobutyl trimethoxysilane; various difunctional silane compounds such as dimethyl dimethoxysilane, dimethyl diethoxy silane, diethyl diethoxy silane, diphenyldimethoxy silane; low molecular weight silanol compounds obtained byvirtually complete hydrolysis of the trifunctional and difunctionalsilane compounds mentioned above, or of the various halo silanes such asmethyl trichloro silane, phenyl trichloro silane, ethyl trichlorosilane, dimethyl dichloro silane, and diplienyl dichloro silane; linearor cyclic polysiloxanes containing silanol functionality, obtained bycarrying out a dehydration condensation on the silanol compoundsmentioned above; and linear or cyclic polysiloxanes containingalkoxysilyl functionality, obtained by carrying out a partial hydrolysiscondensation on at least one of the compounds from the group ofaforementioned difunctional and trifunctional silane compounds andsilicate compounds.

Concerning the amount of aforementioned compound (F), containinghydrolysable silyl and/or silanol functionality, which should be furtheradded to each of the resin compositions comprising compound (B)containing both epoxy and hydrolysable silyl functionalities, and thevarious water based products (A), (C), (D) or (E), to provide thecurable resin compositions for use in water based paint described inthis invention, then for each 100 parts, by weight, of the solidcomponent of the resins from water based products (A), (C), (D) or (E),between 0.5 and 200 parts, by weight, of the compound (F) should beadded, with between I and 100 parts being preferable.

Furthermore, if necessary, a curing catalyst (G) may be added to thecurable resin compositions for use in water based paint described inthis invention. Addition of such a catalyst results in an improvement inthe curability of the compositions.

Representative examples of this catalyst (G) include various basiccompounds such as lithium hydroxide, sodium hydroxide, potassiumhydroxide, and sodium methylate; various metallic compounds such astetraisopropyl titanate, tetra n-butyl titanate, tin octylate, leadoctylate, cobalt octylate, zinc octylate and calcium octylate, zincnaphthenate and cobalt naphthenate, di n-butyl tin diacetate, di n-butyltin dioctoate, di n-butyl tin dilaurate and di n-butyl tin maleate; andvarious acidic compounds such as p-toluenesulfonic acid,tricliloroacetic acid, monoalkyl phosphoric acids, dialkyl phosphoricacids, monoalkyl phosphorous acids and dialkyl phosphorous acids.

Furthermore, if required, various additives may be added to the curableresin compositions for use in water based paint, described in thisinvention. Such additives include various coalescing agents such asisopropyl alcohol, sec-butanol, n-butanol, 2-ethyl hexanol, 2-propoxyethanol, 2-n-butoxy ethanol, 2-n-propoxy propanol, 3-n-propoxy propanol,2-n-butoxy propanol, 3-n-butoxy propanol, 2-n-butoxy ethyl acetate,diethylene glycol monobutyl ether, N-methyl pyrrolidone,2,2,4-trimethyl-1,3-pentanediol monobutarate, dibutyl phthalate esterand butyl benzyl phthalate ester, anti-foaming reagents, organicpigments, inorganic pigments, plasticizers, antioxidants, UV absorber,photostabilising reagents, leveling reagents, anti-streaking reagents,dispersing reagents and thickening reagents.

When using the curable resin compositions for use in water based paintsdescribed in this invention, and outlined above, a so called twocomponent system is used with the constituent compound (B) containingboth epoxy and hydrolysable silyl functionalities, being mixed with theother constituents immediately before use. The mixture should then beused within one day (24 hours), with use inside of 12 hours beingpreferable. Particular care needs to be taken in this respect, as ifleft for more than one day, the room temperature curability of thecomposition decreases markedly.

The curable compositions for use in water based paints described in thisinvention can be used, with conventional methods, to paint varioussurfaces, and then either dried at ambient temperature for between 1 and10 days, force dried at between 40 and 100° C. for between 1 and 60minutes, or bake dried at between 100 and 180° C. for between 1 and 60minutes. This process emits very little organic solvent into theatmosphere and provides a coating film that has excellent weatherresistant and curability properties, and excellent resistance tosolvents, chemicals and water.

The curable resin compositions for use in water based paints describedin this invention then, are novel and yet highly practical, contain no,or very little, organic solvent when compared with current organicsolvent based paints, and yield a cured surface which has excellentweather resistant and curability properties as well as excellentresistance to solvents, chemicals and water.

Consequently, these curable resin compositions for use in water basedpaints, which yield such excellent cured surfaces, are suitable for awide range of uses, including the painting of new vehicles, the repairof vehicles, woods, building, the painting of roof tiles, buildingmaterials, glass and various goods manufactured from plastics, andfurther, in the painting of a variety of metallic materials such asaluminum, stainless steel, chrome plating, corrugated iron and tinnedsheet iron.

EXAMPLES

Next, we will attempt to explain the invention in more concrete terms,by giving reference, working and comparative examples. Note, howeverthat this in no way implies that the invention is limited to theexamples illustrated. Unless specified otherwise, reference in theseexamples to `parts` or `percentages` refers to relative weights.

Reference Example 1 [example of the production of a tertiary amino vinylpolymer (I)]

660 parts of ethylene glycol monoisopropyl ether was placed in areaction vessel fitted with a stirrer, a thermometer, a reflux condenserand a nitrogen gas inlet, and the temperature raised to 80° C., undernitrogen gas atmosphere.

Next, a mixture of 100 parts styrene, 250 parts methyl methacrylate, 480parts n-butyl methacrylate, 70 parts ethyl acrylate, 100 parts dimethylaminoethyl methacrylate, 8 parts of azobis isobuturonitrile, and 5 partstert-butyl peroxy octoate (TBPO) was dripped in slowly over a period of4 hours.

On completion of this addition, the temperature was maintained for afurther 10 hours. The product thus obtained was a solution of thetargeted tertiary amino vinyl polymer (I) (average molecular weight9,500) with a non volatile component of 60%. Hereafter this polymer isabbreviated as polymer (I-1).

Reference Example 2 [example of the production of the water basedproduct (A)]

1.0 part of an 88% water solution of formic acid was added, at roomtemperature, to 100 parts of the polymer (I-1) obtained in referenceexample 1, and the mixture stirred. In this instance a 50%neutralisation rate was obtained.

Next, a further 49 parts of water were added, and stirring continueduntil a uniform mixture was obtained. The product thus obtained was thetargeted water based product, and had a non volatile component of 40%.Hereafter this product is abbreviated as water based product (A-1).

Reference Example 3 [example of the production of the water basedproduct (A)]

2 parts of an 88% water solution of formic acid was added, at roomtemperature, to 100 parts of the polymer (I-1) obtained in referenceexample 1, and the mixture stirred. In this instance a 100%neutralisation rate was obtained.

Next, a further 98 parts of water were added, and stirring continueduntil a uniform mixture was obtained. The product thus obtained was thetargeted water based product, and had a non volatile component of 30%.Hereafter this product is abbreviated as water based product (A-2).

Reference Example 4 [example of the production of a tertiary amino vinylpolymer (I)]

Following the standard method, the polymerisation reaction was carriedout with a mixture of 100 parts styrene, 700 parts n-butyl methacrylate,100 parts ethyl acrylate, 50 parts 2-hydroxy ethyl acrylate and 50 partsdimethyl aminoethyl methacrylate as the monomers, as well as 8 partsazobis isobuturonitrile, and 5 parts tert-butyl peroxy octoate (TBPO),present as polymerisation initiators. This mixture of solvent, monomers,and polymerisation initiators was dripped in slowly over a period of 4hours.

After the completion of this addition, the temperature was maintainedfor a further 10 hours. The product thus obtained was a solution of thetargeted tertiary amino vinyl polymer (I) (average molecular weight9,000) with a non volatile component of 60%. Hereafter this polymer isabbreviated as polymer (I-2).

Reference Example 5 [example of the production of the water basedproduct (A)]

1.0 part of an 88% water solution of formic acid was added, at roomtemperature, to 100 parts of the polymer (I-2) obtained in referenceexample 4, and the mixture stirred. In this instance a 100%neutralisation rate was obtained.

Next, a further 49 parts of water were added, and stirring continueduntil a uniform mixture was obtained. The product thus obtained was thetargeted water based product, and had a non volatile component of 40%.Hereafter this product is abbreviated as water based product (A-3).

Reference Example 6 [example of the production of a tertiary amino vinylpolymer (I)]

Following the standard method, the polymerisation reaction was carriedout using a mixture of 660 parts isopropyl alcohol as solvent, 100 partsstyrene, 700 parts n-butyl methacrylate, 100 parts ethyl acrylate, and100 parts dimethyl aminoethyl methacrylate as the monomers, as well as 8parts azobis isobuturonitrile, and 5 parts tert-butyl peroxy octoate(TBPO), present as polymerisation initiators. This mixture of solvent,monomers, and polymerisation initiators was dripped in slowly over aperiod of 4 hours.

After the completion of this addition, the temperature was maintainedfor a further 10 hours. The product thus obtained was a solution of thetargeted tertiary amino vinyl polymer (I) (average molecular weight9,000) with a non volatile component of 60%. Hereafter this polymer isabbreviated as polymer (I-3).

Reference Example 7 [example of the production of the water basedproduct (A)]

1.1 parts of acetic acid was added, at room temperature, to 100 parts ofthe polymer (I-3) obtained in reference example 6, and the mixturestirred. In this instance a 50% neutralisation rate was obtained.

Next, a further 90 parts of water were added, and stirring continueduntil a uniform mixture was obtained. After this the mixture was heatedto 30° C. to 40° C. and the isopropyl alcohol removed under reducedpressure. The product thus obtained was the targeted water basedproduct, and had a non volatile component of 40%. Hereafter this productis abbreviated as water based product (A-4).

Reference Example 8 [example of the production of a vinyl polymer (II)containing both tertiary amino and acidic functionalities]

Using a mixture of 100 parts styrene, 250 parts methyl methacrylate, 440parts n-butyl methacrylate, 150 parts ethyl acrylate, 40 parts dimethylaminoethyl methacrylate, and 20 parts acrylic acid as the monomers, aswell as 10 parts TBPO as the polymerisation initiator, and otherwisecarrying out the reaction in an identical manner to that described inreference example 1 above, a solution of the targeted vinyl polymer (II)containing both tertiary amino and acidic functionalities (averagemolecular weight 8,000) with a non volatile component of 60% wasobtained. Hereafter this polymer is abbreviated as polymer (II-1).

Reference Example 9 [example of the production of the water basedproduct (C)]

0.8 parts of an 88% water solution of formic acid was added, at roomtemperature, to 100 parts of the polymer (II-1) obtained in referenceexample 8, and the mixture stirred.

Next, a further 49.2 parts of water were added, and stirring continueduntil a uniform mixture was obtained. The product thus obtained was thetargeted water based product, and had a non volatile component of 40%.Hereafter this product is abbreviated as water based product (C-1).

Reference Example 10 [example of the production of the water basedproduct (D)]

1.7 parts of triethyl amine were added, at room temperature, to 100parts of the polymer (II-1) obtained in reference example 8, and themixture stirred. 48.7 parts of water were then added and stirringcontinued until a uniform dispersion was obtained. The product thusobtained was the targeted water based product, and had a non volatilecomponent of 40%. Hereafter this product is abbreviated as water basedproduct (D-1).

Reference Example 11 [example of the production of a vinyl polymer (II)containing both tertiary amino and acidic functionalities]

Using a mixture of 100 parts styrene, 250 parts methyl methacrylate, 340parts n-butyl methacrylate, 150 parts ethyl acrylate, 100 parts2-hydroxyethyl acrylate, 40 parts dimethyl aminoethyl methacrylate, and20 parts acrylic acid as the monomers, as well as 10 parts TBPO as thepolymerisation initiator, and otherwise carrying out the reaction in anidentical manner to that described in reference example 1 above, asolution of the targeted vinyl polymer (II) containing both tertiaryamino and acidic functionalities (average molecular weight 8,000) with anon volatile component of 60% was obtained. Hereafter this polymer isabbreviated as polymer (II-2).

Reference Example 12 [example of the production of the water basedproduct (D)]

1.7 parts of triethyl amine were added, at room temperature, to 100parts of the polymer (II-2) obtained in reference example 11, and themixture stirred. 48.7 parts of water were then added and stirringcontinued until a uniform dispersion was obtained. The product thusobtained was the targeted water based product, and had a non volatilecomponent of 40%. Hereafter this product is abbreviated as water basedproduct (D-2).

Reference Example 13 [example of the production of a vinyl polymer (II)containing both tertiary amino and acidic functionalities]

Using a mixture of 666 parts isopropyl alcohol as solvent, 100 partsstyrene, 690 parts n-butyl methacrylate, 127 parts ethyl acrylate, 33parts dimethyl aminoethyl methacrylate, and 50 parts acrylic acid as themonomer mixture, and 10 parts TBPO as the polymerisation initiator, andotherwise carrying out the reaction in an identical manner to thatdescribed in reference example 1 above, a solution of the targeted vinylpolymer (II) containing both tertiary amino and acidic functionalities(average molecular weight 8,000) with a non volatile component of 60%was obtained. Hereafter this polymer is abbreviated as polymer (II-3).

Reference Example 14 [example of the production of the water basedproduct (D)]

2.5 parts of triethyl amine were added to 100 parts of the polymer(II-3) obtained in reference example 13, and the mixture stirred. 69parts of water were then added and stirring continued until a uniformdispersion was obtained.

Next, the mixture was heated to between 30 and 40° C. and the isopropylalcohol, used as the polymerisation solvent, removed under reducedpressure. The product thus obtained was the targeted water basedproduct, and had a non volatile component of 32%. Hereafter this productis abbreviated as water based product (D-3).

Reference Example 15 [example of the production of a vinyl polymer (III)containing acidic functionalities]

Using a mixture of 666 parts butyl alcohol as solvent, 200 partsstyrene, 500 parts n-butyl methacrylate, 200 parts ethyl acrylate, and100 parts acrylic acid as the monomer mixture, and 10 parts TBPO as thepolymerisation initiator, and otherwise carrying out the reaction in anidentical manner to that described in reference example 1 above, asolution of the targeted vinyl polymer (III) containing acidicfunctionalities (average molecular weight 8,000) with a non volatilecomponent of 60% was obtained. Hereafter this polymer is abbreviated aspolymer (III-1).

Reference Example 16 [example of the production of the water basedproduct (E)]

1.8 parts of N,N dimethyl octyl amine were added to 100 parts of thepolymer (III-1) obtained in reference example 15, and the mixturestirred. 96 parts of water were then added and stirring continued untila uniform dispersion was obtained. The product thus obtained was thetargeted water based product, and had a non volatile component of 30%.Hereafter this product is abbreviated as water based product (E-1).

Reference Example 17 [example of the production of an acidic vinylpolymer (III)]

Using a mixture of 666 parts ethylene glycol mono isopropenyl ether assolvent, 150 parts styrene, 500 parts n-butyl methacrylate, 150 partsethyl acrylate, 100 parts 2-hydroxyethyl acrylate, and 100 parts acrylicacid as the monomer mixture, and 10 parts TBPO as the polymerisationinitiator, and otherwise carrying out the reaction in an identicalmanner to that described in reference example 1 above, a solution of thetargeted acidic vinyl polymer (III) (average molecular weight 8,000)with a non volatile component of 60% was obtained. Hereafter thispolymer is abbreviated as polymer (III-2).

Reference Example 18 [example of the production of the water basedproduct (E)]

1.8 parts of N,N dimethyl octyl amine were added to 100 parts of thepolymer (III-2) obtained in reference example 17, and the mixturestirred. 96 parts of water were then added and stirring continued untila uniform dispersion was obtained. The product thus obtained was thetargeted water based product, and had a non volatile component of 30%.Hereafter this product is abbreviated as water based product (E-2).

Reference Example 19 [example of the production of a compound containingboth epoxy and hydrolysable silyl functionalities (B)]

800 parts of toluene was placed in a similar reaction vessel to thatdescribed in reference example 1, and the temperature raised to 120° C.under a stream of nitrogen.

Next, a mixture of 416 parts lauryl methacrylate, 284 parts glycidylmethacrylate, 300 parts γ-methacryloyl oxy propyl trimethoxy silane and40 parts TBPO was dripped in slowly over a period of 6 hours.

After the completion of this addition, the temperature was maintainedfor a further 10 hours. The product thus obtained was a solution of thetargeted polymer, containing both epoxy and methoxy silylfunctionalities (epoxy equivalence 1000) with a non volatile componentof 50%. Hereafter this compound is abbreviated as compound (B-1).

Reference Example 20 [example of the production of a vinyl polymercontaining both primary amino and acidic functionalities]

Using a mixture of 100 parts styrene, 250 parts methyl methacrylate, 425parts n-butyl methacrylate, 120 parts ethyl acrylate, 55 partsmethacrylic acid and 50 parts acrylic acid as the monomer mixture,n-butyl acetate as the solvent, and 10 parts TBPO as the polymerisationinitiator, and otherwise carrying out the reaction in an identicalmanner to that described in reference example 1 above, a solution of thevinyl polymer to be used for comparative purposes was obtained. The nonvolatile component of the solution was 60%.

Next, the temperature was lowered to 40° C., 36.3 parts of propyleneimine added, and the mixture allowed to react for 6 hours. At this pointthe acid value of the solid constituent of the resin had fallen to 37.4.

42 parts of triethyl amine were then added at room temperature and themixture stir Next, 755 parts of water were added and stirring continueduntil a uniform dispersion was obtained. The product thus obtained wasthe water based product to be used for comparative purposes, and had anon volatile component of 40%. Hereafter this product is referred to asthe comparative resin.

Working Examples 1-12 and Comparative Examples 1 and 2.

White paints made of the various resin compositions for use in waterbased paints were produced by mixing the various constituents in theratios shown in Table 1.

Next, using a 6 mil applicator, each of the paints was applied to a zincphosphate treated steel sheet; a steel sheet which had already beenpainted with a primer, constituted of an oil free alkyd resin andmelamine resin, and then bake dried (i.e., a prepainted sheet); a slatesheet; and a polypropylene sheet, and then left to dry at ambienttemperature for 7 days to produce a fully cured coating film.

The coating film applied to the polypropylene sheet was separated fromthe sheet and its gelling coefficient was measured, while the coatingfilm applied to the prepainted steel sheet was submitted to the exposuretest, for a period of two years, in the suburbs of Miyazaki city, afterwhich time its weather resistance and resistance to pollution wasevaluated. A summary of these results is also shown in Table 1.

                  TABLE 1                                                         ______________________________________                                        *Table 1 (1-1)                                                                             Working  Working  Working                                                                              Working                                              example 1                                                                              example 2                                                                              example 3                                                                            example 4                               ______________________________________                                        Water based product                                                                        100                                                              (A-1)                                                                         Water based product   100                                                     (A-2)                                                                         Water based product            100                                            (A-3)                                                                         Water based product                   100                                     (A-4)                                                                         [R-930]      24.2     18.5     22.6   23.8                                    UV absorber  0.8      0.6      0.8    0.8                                     γ-GPTMS                                                                              7.2      6.3      3.0.   6.0                                     DBTDL        0.04     0.03     0.04   0.03                                    TSL                   20.0     20.0                                           Paint name   CC01     CC02     CC03   CC04                                    ______________________________________                                         *PAINT COMPOSION                                                              [Table 1: footnotes                                                           [R930] . . . abbreviation for [TIPAQUE R930] [brand name for titanium         oxide produced by Ishihara Sanngyo Kaisya Co., Ltd.                           UV absorber . . . a 1:1 mixture, by weight, of [TINUBIN 765] and [TINUBIN     384] (both brand names, produced by Cibageigy Ltd., Switzerland)              GPTMS . . . abbreviation for glycidoxy propyl trimethoxy silane               DBTDL . . . abbreviation for dibutyl tin dilaurate                            TSL . . . abbreviation for a blend, in a molar ratio of 2:1, of the 2         silicate compounds [TSL8 178] and [TSL8 122] [produced by Toshiba Silicon     Co., Ltd.                                                                

    *Table 1 (1-2)                                                                             Working  Working  Working                                                                              Working                                              example 1                                                                              example 2                                                                              example 3                                                                            example 4                               ______________________________________                                        Paint Name   CC01     CC02     CC03   CC04                                    Gelling coefficient (%)                                                                    94       92       96     94                                      Initiai Gloss (20°)                                                                 80       80       87     78                                      Pencil hardness                                                                            2B       HB       H      2B                                      Gloss retention                                                                            66       76       77     62                                      coefficient, (%)                                                              Solvent resistance                                                                         ∘                                                                          ∘                                                                          ◯                                                                        ∘                           Resistance to acidity                                                                      GOOD                                                             Resistance to alkalinity                                                                   GOOD                                                             Water resistance                                                                           GOOD                                                             Wet adhesion 100      90       100    100                                     Resistance to yellowing                                                                    0.4      0.2      0.I    0.4                                     under heat (Δb)                                                         ______________________________________                                         *COATING FILM PROPERTIES                                                      [Table 1: footnotes                                                           Gelling coefficient (%) . . . This percentage is calculated as 100 times      the ratio of the weight of the paint film, having been separated from the     material and then soaked in acetoile for 24 hours, to the weight of film      prior to soaking in acetone                                                   Pencil hardness . . . This refers to the hardness of [Mitsubishi Uni]         pencil [brand name, produced by Mitsubishi Pencils Co., Ltd.] required to     scratch the coating film.                                                     Gloss retention coefficient (%) . . . This percentage value is calculated     by the formula below. The higher this value, the greater the weather          resistant properties of the coating film;                                     Gloss retention coefficient (%) = G.sub.1 /G.sub.0 × 100                [Note, in this formula G.sub.1 refers to the 60° gloss value (the      percentage of 60° incident light reflected) after 2 years exposure     to the elements, and G.sub.0 refers to the initial 60° gloss value     Solvent resistance . . . A piece of felt soaked in methyl ethyl ketone wa     placed on a sample of the paint film and weighted down with a 500 g           weight. The felt was then rubbed back and forth over the paint surface 10     times and the external appearance of the coating film evaluated by eye.       The evaluation standards used are as follows.                                 ∘ no change                                                       ◯ slight scratches visible                                        Δ marked loss in surface Gloss                                          X dissolution and loss of coating film                                        Resistance to acidity . . . A 5% water solution of sulfuric acid was          dripped on to the film for a period of 24 hours, and the film then washed     with water, and its external appearance evaluated by eye.                     Resistatice to alkalinity . . . A 5% water solution of sodium hydroxide       was dripped on to the film for a period of 24 hours, and the film then        washed with water, and its external appearance evaluated by eye.              Water resistance . . . A sample of the paint film was soaked in warm wate     at 40° C. for a period of one week and the external appearance of      the film then evaluated by eye.                                               Wet adhesion . . . Following soaking in warm water at 40° C. for a     period of one week, a cross cut pattern, consisting of 11 horizontal and      11 vertical cuts at regular intervals, was made on die film's surface and     a stripping test carried out using cellophane tape.                           Resistance to yellowing under heat . . A paint film, cured for 7 days at      room temperature, was placed on a sheet of white material and over baked      at 80° C. for a period of one hour, at which point the yellowing o     the film was measured. The value [b] refers to the difference in the          measured value and that of the white material.                           

    *Table 1 (2-1)                                                                             Working  Working  Working                                                                              Working                                              example 5                                                                              example 6                                                                              example 7                                                                            example 8                               ______________________________________                                        Water based product                                                                        100                                                              (C-1)                                                                         Water based product   100                                                     (D-1)                                                                         Water based product            100                                            (D-2)                                                                         Water based product                   100                                     (D-3)                                                                         [R-930]      24.4     24.6     24.6   19.4                                    UV absorber  0.8      0.8      0.8    0.64                                    γ-GPTMS                                                                              7.6      7.6      7.6    5.8                                     DBTDL        0.04                                                             TSL                   10.0     10.0   10.0                                    N-MP         2.0      2.0      2.0    2.0                                     Paint name   CC05     CC06     CC07   CC08                                    ______________________________________                                         *PAINT COMPOSITION                                                            [Table 1: footnotes                                                           NMP . . . abbreviation for Nmethyl pyrrolidone.                          

    *Table 1 (2-2)                                                                             Working  Working  Working                                                                              Working                                              example 5                                                                              example 6                                                                              example 7                                                                            example 8                               ______________________________________                                        Paint Name   CC05     CC06     CC07   CC08                                    Gelling coefficient (%)                                                                    89       90       96     88                                      Initiai Gloss (20°)                                                                 80       78       88     83                                      Pencil hardness                                                                            2B       B        H      2B                                      Gloss retention                                                                            58       73       78     71                                      coefficient (%)                                                               Solvent resistance                                                                         ∘                                                                          ∘                                                                          ◯                                                                        ∘                           Resistance to acidity                                                                      GOOD                                                             Resistance to alkalinity                                                                   GOOD                                                             Water iesistance                                                                           GOOD                                                             Wet adhesion 98       100      100    85                                      Resistance to yellowing                                                                    0.1      0.1      0.1    0.1                                     under heat (Δb)                                                         ______________________________________                                         *COATING FILM PROPERTIES                                                 

    *Table 1 (3-1)                                                                             Working  Working  Working                                                                              Working                                              example  example  example                                                                              example                                              9        10       11     12                                      ______________________________________                                        Water based product                                                                        100      100                                                     (A-1)                                                                         Water based product            100                                            (B-1)                                                                         Water based product                   100                                     (E-2)                                                                         [R-930]      28.2     23.8     19.6   19.6                                    UV absorber  1.0      0.8      0.6    0.6                                     γ-GPTMS         6.0                                                     γ-GPMDMS                 8.0    8.0                                     Polymer (B-1)                                                                              25.0                                                             DBTDL        0.04                                                             SH-6018      2.0      2.0      2.0    2.0                                     Paint name   CC09     CC10     CC11   CC12                                    ______________________________________                                         *PAINT COMPOSITION                                                            [Table 1: footnotes                                                           GPMDMS . . . Abbreviation for glycidoxy propyl methyl dimethoxy silane.       [SH6018] . . . Abbreviation for [Toray Silicone SH6018] a silicone            compound produced by Toray Silicone Co., Ltd.                            

    *Table 1 (3-2)                                                                             Working  Working  Working                                                                              Working                                              example  example  example                                                                              example                                              9        10       11     12                                      ______________________________________                                        Paint Name   CC09     CC10     CC11   CC12                                    Gelling coefficient (%)                                                                    95       92       94     96                                      Initial Gloss (20°)                                                                 72       80       80     87                                      Pencil hardness                                                                            4B       2B       F      2H                                      Gloss retention                                                                            63       74       58     69                                      coefficient (%)                                                               Solvent resistance                                                                         ∘                                                                          ∘                                                                          ◯                                                                        ∘                           Resistance to acidity                                                                      GOOD                                                             Resistance to alkalinity                                                                   GOOD                                                             Water resistance                                                                           GOOD                                                             Wet adhesion 100      100      80     70                                      Resistance to yellowing                                                                    0.3      0.3      0.1    0.1                                     under heat (Δb)                                                         ______________________________________                                         *COATNG FILM PROPERTIES                                                  

    *Table 1 (4-1)                                                                                   Comparative                                                                             Comparative                                                         example 1 example 2                                        ______________________________________                                        Polymer (I-1)                100                                              Comparative resin  100                                                        Titanium Oxide R-930                                                                             26.2      35.7                                             UV absorber        0.8       1.2                                              γ-GPTMS      12.4      9.0                                              DBTDL              0.04      0.06                                             N-MP               2.0                                                        Solvent mixture              43                                               Paint name         CC'01     CC'02                                            ______________________________________                                         *PAINT COMPOSITION                                                            [Table 1: footnotes                                                           Solvent mixture . . . This is a 70/30 mixture by weight, of toluene and       nbutyl acetate.                                                          

    *Table 1 (4-2)                                                                                   Comparative                                                                             Comparative                                                         example 1 example 2                                        ______________________________________                                        Paint Name         CC'01     CC'02                                            Gelling coefficient (%)                                                                          80        95                                               Pencil hardness    2B        B                                                Gloss retention coefficient (%)                                                                  20        66                                               Solvent resistance X         Δ                                          Resistance to acidity                                                                            GOOD                                                       Resistance to alkalinity                                                                         GOOD                                                       Water resistance   GOOD                                                       Wet adhesion       0         100                                              Resistance to yellowing under                                                                    0.2       3                                                heat (Δb)                                                               ______________________________________                                         *COATING FILM PROPERTIES                                                 

We claim:
 1. A curable resin composition for use in water based paintscomprising;a water based product (D) obtained by dispersing ordissolving in water, a vinyl polymer (II) containing both tertiary aminofunctionalities in an amount between 0.05 and 1.5 moles per 1000 gramsof solid material and acidic functionalities in an amount between 0.07and 2.0 moles per 1000 grams of solid material, to which has been addedsufficient basic compound so that the molar ratio of basicfunctionalities in the added basic compound to acidic functionalities inthe vinyl polymer (II) is at least 0.1, and a compound (B) containingboth epoxy and hydrolysable silyl functionalities, wherein the molarratio of the total of the tertiary amino functionalities and the acidicfunctionalities in the water based product (D) to the epoxyfunctionalities in the compound (B) is between 0.3 and 3.0.
 2. A curableresin composition for use in water based paints comprising;a water basedproduct (D) obtained by dispersing or dissolving in water, a vinylpolymer (II) containing both tertiary amino functionalities in an amountbetween 0.05 and 1.5 moles per 1000 grams of solid material and acidicfunctionalities in an amount between 0.07 and 2.0 moles per 1000 gramsof solid material, to which has been added sufficient basic compound sothat the molar ratio of basic functionalities in the added basiccompound to acidic functionalities in the vinyl polymer (II) is at least0.1, a compound (B) containing both epoxy and hydrolysable silylfunctionalities, and a curing catalyst (G), wherein the molar ratio ofthe total of the tertiary amino functionalities and the acidicfunctionalities in the water based product (D) to the epoxyfunctionalities in the compound (B) is between 0.3 and 3.0.
 3. A curableresin composition according to claim 1, wherein the number-averagemolecular weight of the vinyl polymer (II) is in the range of 1,000 to30,000.
 4. A curable resin composition according to claim 2, wherein thenumber-average molecular weight of the vinyl polymer (II) is in therange of 1,000 to 30,000.
 5. A curable resin composition according toclaim 1, wherein the ratio of the equivalent number of the basicfunctionalities in the basic compound to the equivalent number of theacidic functionalities in the vinyl polymer (II) is in the range of 0.1to 3.0.
 6. A curable resin composition according to claim 2, wherein theratio of the equivalent number of the basic functionalities in the basiccompound to the equivalent number of the acidic functionalities in thevinyl polymer (II) is in the range of 0.1 to 3.0.